Second generation catalytic asymmetric synthesis of tamiflu: Allylic substitution route

Organic Letters

Volumn 9, Issue 2, 2007, Pages 259-262

  Mita, Tsuyoshi ^a   Fukuda, Nobuhisa ^a   Roca, Francesc X ^a   Kanai, Motomu ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

LIGAND; ORGANOMETALLIC COMPOUND; OSELTAMIVIR; YTTRIUM;

ARTICLE; CATALYSIS; CHEMISTRY; CONFORMATION; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; LIGANDS; MOLECULAR CONFORMATION; ORGANOMETALLIC COMPOUNDS; OSELTAMIVIR; STEREOISOMERISM; YTTRIUM;

EID: 33846647467     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol062663c     Document Type: Article

References (19)

1. Kim, C. U.; Lew, W.; Williams, M. A.; Liu, H.; Zhang, L.; Swaminathan, S.; Bischofberger, N.; Chen, M. S.; Mendel, D. B.; Tai, C. Y.; Laver, W. G.; Stevens, R. C. J. Am. Chem. Soc. 1997, 119, 681.
2. For a recent review of synthetic strategies of Tamiflu, see: Farina, V.; Brown, J. D. Angew. Chem., Int. Ed. 2006, 45, 7330.
3. Abrecht, S.; Harrington, P.; Iding, H.; Karpf, M.; Trussardi, R.; Wirz, B.; Zutter, U. Chimia 2004, 58, 621.
4. Yeung, Y.-Y.; Hong, S.; Corey, E. J. J. Am. Chem. Soc. 2006, 128, 6310.
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6. (a) Bartlett, P. A.; McQuaid, L. A. J. Am. Chem. Soc. 1984, 106, 7854.
7. (b) Kurihara, T.; Miki, M.; Yoneda, R.; Harusawa, S. Chem. Pharm. Bull. 1986, 34, 2747.
8. Previously, 4 was produced in 96% yield with 91% ee, using 2 mol % of the catalyst in the absence of 2,6-dimethylphenol (reaction time = 48 h). For beneficial effects of a protic additive in a catalytic asymmetric conjugate addition of an azide, see: Guerin, D. J.; Miller, S. J. J. Am. Chem. Soc. 2002, 124, 2134.
9. Dalko, P. I.; Langlois, Y. Tetrahedron Lett. 1998, 39, 2107.
10. Yamada, S.; Kasai, Y.; Shioiri, T. Tetrahedron Lett. 1973, 1595.
11. Harusawa, S.; Yoneda, R.; Kurihara, T.; Hamada, Y.; Shioiri, T. Tetrahedron Lett. 1984, 25, 427.
12. Configuration of the tetrasubstituted carbon of 15 was temporarily assigned as shown based on the structure of 29 (see Scheme 4).
13. Pd(II)-catalyzed allylic rearrangement (ref 6a) did not afford the desired product.
14. Ho, M.; Chung, J. K. K.; Tang, N. Tetrahedron Lett. 1993, 34, 6513.
15. Ring-opening reaction of cyclic carbamate 16 with 3-pentanol was intensively studied in the presence of a variety of Lewis acids. The desired product, however, was not produced in these reactions.
16. Harrington, P. J.; Brown, J. D.; Foderaro, T.; Hughes, R. C. Org. Process Res. Dev. 2004, 8, 86.
17. Shangguan, N.; Katukojvala, S.; Greenberg, R.; Williams, L. J. J. Am. Chem. Soc. 2003, 125, 7754.
18. The stereochemistry of the allylic position of 28 was temporarily assigned based on Bartlett and Kurihara's previous findings (ref 6), in which allylic rearrangement of α-cyanophosphate proceeded in a suprafacial fashion.
19. Neither direct addition of 3-pentanol to 28 nor aziridine formation from 28 proceeded under various conditions.